Sample viscosity and flow control for heavy samples, and x-ray analysis applications thereof

ABSTRACT

An x-ray analysis system having an x-ray engine with an x-ray source for producing an x-ray excitation beam directed toward an x-ray analysis focal area; a sample chamber for presenting a sample stream to the x-ray analysis focal area, the analysis focal area disposed within a sample analysis area defined within the chamber; an x-ray detection path for collecting secondary x-rays and directing the x-rays toward a detector; an x-ray transparent barrier on a wall of the chamber through which the x-rays pass; and a blocking structure partially blocking the sample analysis area, for creating sample stream turbulence in the sample analysis area and over the barrier. The blocking structure may be disposed asymmetrically about a central axis of the x-ray analysis focal area and/or the sample analysis area; and may be a rounded pin. A heating element may be used to heat the sample stream for improving flow.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/584,978, filed Aug. 14, 2012, which published Feb. 21, 2013, as U.S.Patent Publication No. 2013/0044858 A1, and which also claims thebenefit of United States provisional patent application Ser. No.61/523,605, filed Aug. 15, 2011, each of which is hereby incorporatedherein by reference in its entirety.

TECHNICAL FIELD

This invention relates in general to apparatus and methods used forx-ray analysis of sample streams. More particularly, the presentinvention is directed to viscosity and flow control techniques forpresenting a heavy sample stream to an x-ray analysis focal area in anx-ray analysis system.

BACKGROUND OF THE INVENTION

X-ray analysis of samples is a growing area of interest across manyindustries such as medical, pharmaceutical, and petroleum. The use ofx-ray fluorescence, x-ray diffraction, x-ray spectroscopy, x-rayimaging, and other x-ray analysis techniques has led to a profoundincrease in knowledge in virtually all scientific fields.

X-ray fluorescence (XRF) is an analytical technique by which a substanceis exposed to a beam of x-rays to determine, for example, the presenceof certain components. In XRF, at least some of the elementalconstituents of the substance exposed to x-rays can absorb x-ray photonsand produce characteristic secondary fluorescence. These secondaryx-rays are characteristic of the elemental constituents in thesubstance. Upon appropriate detection and analysis these secondaryx-rays can be used to characterize one or more of the elementalconstituents. XRF techniques have broad applications in many chemicaland material science fields, including industrial, medical,semiconductor chip evaluation, petroleum, and forensics, among others.

As some examples of measurements required in the petroleum industry,trace levels of contaminants in petroleum feedstocks is a notoriousproblem in petroleum refining. Sulfur is a common component in crude oilstreams—and its removal from final product is mandated due to its impacton the environment, as regulated by the US EPA under the Clean Air Act.Sulfur is harmful to the environment, and the cost of its removal ishigh. Therefore, monitoring sulfur levels early in the refining processis important. Chlorine and vanadium contaminants are considered “badactors” by the refining industry for primarily non-regulatory, processcontrol reasons. Chlorides also pose one of the greatest problems to therefining industry. According to a 2005 paper by The National Associationof Corrosion Engineers (“NACE”): “Recently, an increasing number ofrefineries have experienced extreme corrosion and fouling in crudedistillation unit overheads and/or naphtha hydrotreating units. The rootcauses were traced to severe spikes in the chloride levels.”

U.S. Pat. Nos. 6,934,359 and 7,072,439, hereby incorporated by referenceherein in their entirety and assigned to X-Ray Optical Systems, Inc.,the assignee of the present invention, disclose monochromatic wavelengthdispersive x-ray fluorescence (MWD XRF) techniques and systems for theanalysis of liquid samples. Moreover, commonly assigned U.S. Pat. No.7,277,527 (also included by reference in its entirety) entitled “MOVABLETRANSPARENT BARRIER FOR X-RAY ANALYSIS OF A PRESSURIZED SAMPLE”addresses a particular problem inherent in moving sample streams in suchsystems as discussed further below.

As one particular example of a measurement system for such contaminants,the above-incorporated patents disclose techniques for the determinationof the level of elements in petroleum fuels, and a commercializedanalyzer (SINDIE) is now in widespread use for, e.g., sulfur measurementat petroleum refining, pipeline, and terminal facilities.

XRF fluid testing can take place off-line, i.e., using a bench-top,laboratory-type instrument to analyze a sample. The material is removedfrom its source (e.g., for fuel, from a refinery or transportationpipeline) and then simply deposited in a sample chamber; or into awindowed sample cell which is then deposited into a chamber. Off-line,bench-top instruments need not meet any unusualoperational/pressure/environmental/size/weight/space/safety constraints,but merely need to provide the requisite measurement precision for amanually-placed sample. Moreover, off-line instruments can be easilymaintained between measurements.

In contrast to off-line analysis, on-line analysis provides “real-time”monitoring of sample composition at various points in the manufacturingprocess. For example, all fuel products are subject to sulfur levelcompliance—requiring some variant of on-line monitoring during fuelrefining and transportation in pipelines. On-line analysis of fuels in arefinery and in pipelines, however, requires consideration of numerousoperational issues not generally present in an off-line, laboratorysetting. A fully automated fuel sample handling system is required—withlittle or no manual intervention or maintenance. Also, since fluids areusually under pressure in pipelines, any sample handling system mustaccount for pressure differentials. This is especially important sincecertain portions of XRF x-ray “engines” (discussed further below)operate in a vacuum. Also, the instrument's electronics requirepackaging in an explosion-proof housing—separate from the samplehandling system.

In an on-line analyzer for crude and heavy fuel applications, differingsample stream viscosities make it challenging to present samples to theanalyzer at a stable pressure and flow rate. Chlorine measurementpresents another challenge because the chlorine mostly exists in waterphase, which may not mix homogeneously in crude.

In these applications one of the most critical components is the samplebarrier(s) which allow photons of the x-rays to excite sulfur atoms inthe fluid, and photons emitted from the atoms to be counted at theengine's detector, while at the same time maintaining the vacuum in thex-ray engine and the pressure of the fluid. X-ray stimulation may createsulfur (or other hard element) ionization and adsorption at thisinterface over time and on certain types of barrier materials—leading toundesired sulfur residue and degradation of the barrier's x-raytransparency. More generally, many XRF applications require a barrier toprotect the engine from any number of adverse interface effects from thesample material and/or the measurement environment.

The barrier system of above-incorporated U.S. Pat. No. 7,277,527 offereda very important and successful solution to these problems in the formof a moveable barrier advanced at programmable intervals to cleanportions of a window roll, however, it is still desirable to providetechniques which keep this interface clean, and the sample stream movingthrough the sample cell at a desirable rate and consistency.

What is required, therefore, are lower cost and lower maintenance samplehandling techniques for an on-line x-ray analysis system handling highviscosity samples, which protects the x-ray engine from adverse sampleand environmental effects, while maintaining the integrity andtransparency of the interface to the sample for accurate measurementswithout excessive moving parts.

SUMMARY OF THE INVENTION

The shortcomings of the prior art are overcome and additional advantagesare provided by the present invention which in one aspect is an x-rayanalysis system having an x-ray engine with an x-ray source forproducing an x-ray excitation beam, the x-ray excitation beam directedtoward an x-ray analysis focal area; a sample chamber for presenting asample stream to the x-ray analysis focal area, the x-ray analysis focalarea disposed within a sample analysis area defined within the chamber;an x-ray detection path for collecting secondary x-rays from the focalarea and directing the secondary x-rays toward a detector; an x-raytransparent barrier on a wall of the chamber through which the x-rayexcitation beam and the secondary x-rays pass; and a blocking structurepartially blocking the sample analysis area, for creating sample streamturbulence in the sample analysis area and over the barrier.

The blocking structure may be disposed asymmetrically about a centralaxis of the x-ray analysis focal area and/or the sample analysis area;and may be a rounded pin.

In one embodiment, a heating element may be used to heat the samplestream for improving flow of the sample stream.

The focal area may be a focal point, defined by focused x-rays to/fromat least one focusing optic in the x-ray excitation path and/or thex-ray detection path. The focusing optic may be a curved diffractingoptic or a polycapillary optic.

The system may comprise a monochromatic wavelength-enabled XRF analyzer;e.g., an MWDXRF or ME-EDXRF analyzer.

The sample may comprise a low or high viscosity petroleum-based productrequiring the measurement of an analyte therein, e.g., one or moreelements chosen from the following list: S, Cl, P, K, Ca, V, Mn, Fe, Co,Ni, Cu, Zn, Hg, As, Pb, and Se.

Further, additional features and advantages are realized by thetechniques of the present invention. Other embodiments and aspects ofthe invention are described in detail herein and are considered a partof the claimed invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter regarded as the invention is particularly pointed outand distinctly claimed in the claims at the conclusion of thespecification. The foregoing and other objects, features, and advantagesof the invention are apparent from the following detailed descriptiontaken in combination with the accompanying drawings in which:

FIG. 1 is a functional block diagram of the elements of an exemplaryx-ray fluorescence system;

FIG. 2 is an isometric view of an exemplary x-ray fluorescencesource/detection “engine” with an exemplary sample chamber;

FIG. 3 is a schematic view of an MWD XRF analysis engine in combinationwith a sample chamber having a moving sample stream; and

FIG. 4 is an isometric, solid view of a dynamic window module;

FIGS. 5 a-b are partial cross-sectional views of an improved samplechamber in accordance with the present invention; and

FIG. 6 is a manifold showing a potential application of heat tape to theinput sample stream, in accordance with the principles of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 is a functional block diagram of a typical MWD XRF system 10 usedfor exposing a sample to x-ray radiation to produce fluorescentradiation which can then be detected and analyzed to determine acharacteristic of the sample. The system may include an x-ray source 12,a first x-ray focusing device 14, a sample chamber 16, a second x-rayfocusing device 18, and an x-ray detector 20. The x-ray source 12, forexample, an x-ray tube, produces a beam of x-rays 22. Though x-rays areused throughout the specification, the invention extends to neutron,particle-beam or gamma ray radiation. Beam 22 may diffracted or focusedby means of one or more x-ray focusing optics 14 as discussed furtherbelow.

The sample under test in sample chamber 16 may be any desired substancefor which a characteristic measurement is desired. If the sample isstatic (in, for example, an off-line system), the sample is typicallylocated on a relatively flat surface, for example, an x-ray reflectiveflat surface or an optically-reflective surface. The sample, if a solid,liquid, or gas, may also be contained in a closed container or chamber,for example, a sealed container, having an x-ray transparent aperturethrough which x-ray beam can pass. The present invention is directed to,in general, low or high viscosity samples in streamable form (e.g.,particulate, powders, liquid, gas, or a liquid-based material (e.g.slurry with particulate matter)) required to be moved through a chamber,and which exert some other potentially disruptive forces or effectswithin the chamber.

When irradiated by beam 24, at least one of the constituents of samplein chamber 16 is excited in such a fashion that the constituentfluoresces, that is, produces a secondary source of x-rays 26 due toexcitation by x-rays 24. Again, since x-ray beam 26 is typically adiverging beam of x-rays, beam 26 is focused by means of the secondx-ray focusing device 18, for example, a device similar to device 14, toproduce a focused beam of x-rays 28 directed toward x-ray detector 20.

X-ray detector 20 may be a proportional counter- type or a semiconductortype x-ray detector (e.g., silicon drift detector), or any othersuitable type of x-ray fluorescence detector known to one skilled in theart. Typically, x-ray detector 20 produces an electrical signal 30containing at least some characteristic of the detected x-rays which isforwarded to an analyzer 32 for analysis, printout, or other display.

FIG. 2 illustrates an MWD XRF x-ray engine assembly 110 according to theabove-incorporated U.S. Pat. No. 7,072,439 entitled “X-RAY TUBE ANDMETHOD AND APPARATUS FOR ANALYZING FLUID STREAMS USING X-RAYS.” This isan example of a sulfur in fuels analysis system, and also employing theprinciples of monochromatic X-Ray excitation and collection as set forthin the above-incorporated U.S. Pat. No. 6,934,359 entitled “WAVELENGTHDISPERSIVE XRF SYSTEM USING FOCUSING OPTIC FOR EXCITATION AND A FOCUSINGMONOCHROMATOR FOR COLLECTION.” X-ray engine assembly 110 (shown with itshousing removed) comprises an x-ray source assembly 112, a samplechamber interface 116 and an x-ray detector assembly 120. A curvedcrystal, monochromating and focusing optic 114 is shown in theexcitation path, along with another curved crystal focusing optic 118 inthe detection path. X-ray source assembly 112 produces an x-ray beam 122which is focused by x-ray focusing optic 114 to produce a focused beam124 on a sample under test in chamber assembly 116. The x-rayfluorescence created by the x-ray irradiation of the sample in sampleexcitation chamber assembly 116 generates x-ray fluorescent beam 126.Beam 126 is focused by x-ray focusing device 118 to provide a focusedx-ray beam 128 which is directed to x-ray detector assembly 120.

The x-ray optics may include, for example, curved crystal monochromatingoptics such as those disclosed in commonly assigned U.S. Pat. Nos.6,285,506; 6,317,483; 7,035,374; and 7,738,629; and/or multilayeroptics; and/or polycapillary optics such as those disclosed in commonlyassigned U.S. Pat. Nos. 5,192,869; 5,175,755; 5,497,008; 5,745,547;5,570,408; and 5,604,353. Optic/source combinations such as thosedisclosed in commonly assigned U.S. Pat. Nos. 7,110,506; 7,209,545; and7,257,193 are also useable. Each of the above-noted patents is herebyincorporated herein by reference in its entirety.

Exemplary curved monochromating optics in the excitation and detectionpaths are shown in FIG. 2, which is the engine configuration of theSINDIE sulfur analyzer discussed above. However, an optic may only bepresent in one of these paths, which still requires precise alignment.In one example, an optic of any of the above-described types may only bepresent in the excitation path, and the detection path would include anenergy dispersive detector. This is the configuration of a monochromaticexcitation, energy dispersive x-ray fluorescence (ME-EDXRF) system.On-line, monochromatic excitation, energy dispersive x-ray fluorescenceanalyzers can also be used for these applications, in accordance withthe present invention. The engine technology is disclosed in, e.g.,commonly assigned PCT Publication No. WO 2009111454 (A1) entitled “XRFSYSTEM HAVING MULTIPLE EXCITATION ENERGY BANDS IN HIGHLY ALIGNEDPACKAGE,” the entirety of which is hereby incorporated by referenceherein. In one embodiment this technique involves monochromaticexcitation known as HD XRF. HD XRF is a multi-element analysis techniqueoffering certain enhanced detection performance over traditional ED orWD XRF. This technique applies state-of-the-art monochromating andfocusing optics, enabling multiple select-energy excitation beams thatefficiently excite a broad range of target elements in the sample.Monochromatic excitation dramatically reduces scattering backgroundunder the fluorescence peaks, greatly enhancing elemental detectionlimits and precision. HDXRF is a direct measurement technique and doesnot require consumables or special sample preparation. Exemplaryspecifications for improved on-line analyzers usingmonochromatic-enabled x-ray excitation (including but not limited toME-EDXRF and MWDXRF) include but are not limited to:

Exemplary elements measured: S, Cl, P, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn,Hg, As, Pb, and/or Se.

Sample T>cloud point, max 250 deg. F

Viscosity 20 cSt or more

Filtration: 100 um

LOD: 0.3 ppm @300 s—aqueous matrix

LOD: 0.2 ppm @300 s—hydrocarbon matrix

Analysis Time: 10-900 s—user adjustable

Exemplary Range: 0.2 ppm/wt—3,000 ppm/wt

(One of the key benefits of the disclosed on-line analyzer is itsability to measure both organic and inorganic chlorides.)

In certain methods of XRF detection, the sample excitation path anddetection path are maintained in an inert gas atmosphere, for example,in a helium atmosphere. However, the unavailability of inert gases,especially in remote locations, makes the implementation of these priorart processes inconvenient. In contrast, here the sample excitation pathand the detection path may be maintained under vacuum and no inert gasis necessary. For example, the radiation paths of system 110 shown inFIG. 2 may be held under vacuum, for example, at least about 15 torr.The vacuum can be provided by a venturi pump having no moving parts.However, if desired and available, an inert gas such as nitrogen orhelium can be introduced and maintained in a housing, for example, underpressure.

The use of a vacuum enclosing the x-ray engine (e.g., source, excitationpath, collection path, and detector) leads to certain problems at thesample interface—at the respective focal spots of beams 124 and 126. InFIG. 2, the engine's interface to the sample chamber 116 (discussedfurther below) may consist of a beryllium or kapton window barrier—whichis strong and has the requisite x-ray transparency. But, additionallevels of transparency are required when the sample chamber and itsoperational environment present certain operational difficulties asdiscussed above, especially in on-line systems.

FIG. 3 depicts in schematic view an exemplary MWD XRF x-ray analysisengine 200, in combination with a sample chamber 260 carving a samplestream 270. As discussed above, the x-ray analysis engine may involve afocal area (created by excitation and/or detection optics) requiringalignment with the sample in the sample chamber. As discussed above.engine 200 includes, in one embodiment, an x-ray source 210 and detector250. X-ray optics 220 and/or 240 can be placed in the excitation and/ordetection paths of the engine. These optics require a high degree ofalignment with the sample focal area to function at the requisite limitsof detection discussed above.

Optic 220 focuses and monochromates the excitation x-rays 222 from thesource 210 to a focal area 280 within the sample chamber 260. Optic 240may also be used to focus the secondary fluorescence x-rays 242 from thefocal area 280 to the detector 250. The excitation x-rays 222 andfluorescence x-rays 242 pass through an engine window barrier 290 (e.g.,beryllium) and chamber barrier 262 to the focal area 280 within thechamber 260 and through which sample stream 270 flows. “Focal area” isused broadly herein to connote a sample analysis area to/from whichx-rays are directed. In one embodiment, the focal area could be a smallfocal point with a diameter between 1-2 mm (or smaller) formed byconverging excitation and/or fluorescence x-rays.

In this figure, the sample is presented into the sample chamber as asample stream 270. The sample stream flows over the chamber's barrier262 in this embodiment. The sample chamber could be part of a largerflow pipe system, a section of which is depicted in FIG. 3, and/or couldbe a relatively confined space (as discussed further below) with asample inlet and outlet. Therefore, the term “sample chamber” is usedbroadly herein to connote any type of apparatus within which a samplestream can be defined, near the x-ray engine. The word “through” isbroadly used herein to connote the stream passing directly through thefocal area, or proximate thereto, with proximity being adequate enoughto create the stimulation and/or fluorescent x-rays as required in aworkable x-ray system.

As discussed above, adsorption and other effects at the sample chamberbarrier may impede proper measurement at this interface. With referenceto FIG. 4, an improved sample handling apparatus, or “dynamic windowmodule” 310 is depicted which is particularly suited to handle certainadverse conditions characteristic of on-line systems, in accordance withabove-incorporated U.S. Pat. No. 7,277,527. The apparatus includes asample chamber 320 having input 322 and output 324 sample ports for,e.g., particulate, liquid or gas moving through the system underpressure and requiring measurement. The apparatus includes a moveablebarrier film 340 wound around a feed reel 342 and a take-up reel 344.The film, as discussed further below, runs past a sample aperture in acavity at the bottom face of the chamber 320 (in fluid communicationwith the input and output ports) and provides an x-ray transparentbarrier between the sample chamber and the x-ray engine discussedelsewhere herein. The barrier maintains compatibility with theenvironment from which the sample is drawn (e.g., pressurized) whilemaintaining the integrity of the x-ray engine, possibly itself under avacuum.

In the embodiment shown, the take-up reel can be driven by aremotely-controlled motor 350 to move the film past a sample aperture atthe bottom face of the chamber. A trigger wheel 352 and photo-electricsensor 354 can be used to remotely sense and report the amount ofmovement—using standard connections to a computer network (not shown).In this exemplary embodiment, the barrier movement may not be acontinuous movement during sample measurement, rather, may eitherpartially or fully “refresh” or “replace” areas of the barrier worn-outby adverse conditions, while maintaining the operating environments ofboth the x-ray engine and the sample handling apparatus.

In accordance with the present invention, and with reference to thepartial cross-sectional views of FIGS. 5 a-b, an improved sample chamber420 is provided. As above, the chamber includes input 422 and output 424sample ports for, e.g., particulate, liquid or gas 470 moving throughthe system under pressure and requiring measurement in sample area 460.Moveable sample barrier 440 may separate the chamber 420 from the x-rayengine assembly 400 (portions of which are not shown but may beimplemented in accordance with any of the above described techniques).Focal area 480 is defined by, e.g., the x-ray engine/optics discussedabove for analyzing sample flowing through sample area 460. Sample area460, formed in this example by the intersection of ports 422 and 424, isdisposed over focal area 480. In accordance with the present invention,the otherwise unimpeded intersection of ports in sample area 460 isinterrupted by a partial blocking structure 468.

With particular reference to the enlarged view of FIG. 5 b, thisblocking structure 468 significantly blocks sample flow in the uppersection of sample area 468, while inducing increased sample flow ratedirectly proximate the focal area 480 and over barrier 440; or otherwisecausing sample turbulence in this area. This increased sample flow rateand/or sample turbulence acts as a flushing mechanism to inhibitprecipitate and/or other contamination of barrier 440 proximate focalarea 480. Blocking structure may be implemented using any physicalstructure adequate to create the required turbulence, integrally formedin the chamber or otherwise affixed in the chamber. The structure shownin FIGS. 5 a-b is a rounded (e.g., circular) pin, inserted into theotherwise uniform intersection area of ports 422 and 424; however, anysuitable shape may be employed for the blocking structure. Also in theexemplary embodiment shown, structure 468 is disposed asymmetrically,slightly offset from central axis Z of the sample analysis area and/orx-ray focal area, slightly towards output port 424. This offset createsthe necessary turbulence over focal area 480. Also shown incross-section is o-ring 442, which facilitates a seal around in thesample chamber against barrier 440, in accordance with theabove-incorporated U.S. Pat. No. 7,277,527.

Also in accordance with the present invention, and with reference toFIG. 5 a, heating elements 490 can be applied prior to the sampleanalysis area in the form of, e.g., heat tape and/or heat blocks, and/orany other type of heating structure to modify the temperature of theincoming sample. Heating high viscosity sample streams is especiallyuseful to thin the sample prior to the sample analysis area to enablesmoother sample flows.

As shown in FIG. 6, a manifold 500 may support longer lengths of sampleinput tubes 522, along which longer lengths of heat tape 590 can beplaced, prior to the sample stream's presentation to the sample chamberdiscussed above.

The present invention is especially useful in a real-time, on-linesample flow and analysis system for contaminant monitoring in crude oilsand other heavy fuels, in refining applications. By measuring thesecontaminants real-time, fuel refineries will benefit from extendedoverall uptime, increased process efficiency, and improved safety. Forsuch applications, the principles of the present invention may be usedin combination with any of the disclosures of commonly-assigned U.S.Provisional Patent Application No. 61/498,889 filed on Jun. 20, 2011 andentitled ONLINE MONITORING OF CONTAMINANTS IN CRUDE AND HEAVY FUELS, ANDREFINERY APPLICATIONS THEREOF, the entirety of which is herebyincorporated by reference.

Although preferred embodiments have been depicted and described indetail herein, it will be apparent to those skilled in the relevant artthat various modifications, additions, substitutions and the like can bemade without departing from the spirit of the invention and these aretherefore considered to be within the scope of the invention as definedin the following claims.

What is claimed is:
 1. An x-ray analysis sample handling apparatus,comprising: a sample chamber defining a sample analysis area withinwhich a sample stream flows about an x-ray analysis focal area of anx-ray engine; an x-ray transparent barrier in a wall of said chamber forallowing x-rays to/from the sample analysis area; a blocking structurepartially blocking the sample analysis area, for creating sample streamturbulence in the sample analysis area and over the barrier.
 2. Theapparatus of claim 1, wherein the blocking structure is disposedasymmetrically about a central axis of the x-ray analysis focal areaand/or the sample analysis area.
 3. The apparatus of claims 2, whereinthe blocking structure comprises a rounded pin.
 4. The apparatus ofclaim 1 in combination with an x-ray analysis system, the x-ray analysissystem comprising the x-ray engine including: an x-ray excitation path;and an x-ray detection path; wherein the x-ray excitation and/or thex-ray detection paths define the x-ray analysis focal area in saidchamber.
 5. The combination of claim 4, wherein the focal area is afocal point.
 6. The combination of claim 5, wherein the focal point isdefined by focused x-rays to/from at least one focusing optic in thex-ray excitation path and/or the x-ray detection path.
 7. Thecombination of claim 6, wherein the at least one focusing optic is atleast one curved diffracting optic or polycapillary optic.
 8. Thecombination of claim 6, wherein the at least one focusing optic is atleast one focusing monochromatic optic.
 9. The combination of claim 8,wherein the at least one focusing monochromatic optic is a curvedcrystal optic or curved multi-layer optic.
 10. The combination of claim5, wherein at least one focusing optic in the x-ray detection path ispositioned such that an input focal point thereof is at the x-ray focalpoint, and corresponds to an output focal point of at least one focusingoptic in the x-ray excitation path.
 11. The combination of claim 4,wherein the x-ray analysis system comprises a monochromaticwavelength-enabled XRF analyzer.
 12. The combination of claim 11,wherein the analyzer is an MWDXRF or ME-EDXRF analyzer.
 13. Theapparatus of claim 1, further comprising a heating element to heat thesample stream for improving flow of the sample stream.
 14. The apparatusof claim 1, wherein the sample comprises a petroleum-based productrequiring the measurement of an analyte therein.
 15. The apparatus ofclaim 1, wherein an analyte measured is at least one element chosen fromthe following list: S, Cl, P, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Hg, As,Pb, and Se.
 16. The apparatus of claim 1, wherein the stream is crudeoil, and an analyte measured is chlorine.
 17. An x-ray analysis systemcomprising: an x-ray engine having an x-ray source for producing anx-ray excitation beam, the x-ray excitation beam directed toward anx-ray analysis focal area; a sample chamber for presenting a sample tothe x-ray analysis focal area, the x-ray analysis focal area disposedwithin a sample analysis area defined within the chamber; an x-raydetection path for collecting secondary x-rays from the focal area anddirecting the secondary x-rays toward a detector; an x-ray transparentbarrier on a wall of the chamber through which the x-ray excitation beamand the secondary x-rays pass; and a blocking structure partiallyblocking the sample analysis area, for creating sample stream turbulencein the sample analysis area and over the barrier.
 18. The system ofclaim 17, wherein the analyzer comprises a monochromaticwavelength-enabled XRF analyzer.
 19. The system of claim 18, wherein thesystem is an MWDXRF or ME-EDXRF analyzer.
 20. The system of claim 17,wherein an analyte measured is at least one element chosen from thefollowing list: S, Cl, P, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Hg, As, Pb,and Se.
 21. The system of claim 17, wherein the stream is crude, and ananalyte measured is chlorine.